Process for breaking petroleum emulsions



Patented Feb. 20, 1951 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, St. Louis, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application December 10, 1948, Serial No. 64,446

-, I 19 Claims.

This invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving emulsions of the water-inoil type, and particularly petroleum emulsions. This invention is a continuation-in-part of our co-pending application, Serial No. 734,202, filed March 12, 1947 (now abandoned). See also our co-pending application, Serial No. 8,731, filed February 16, 1948 (now abandoned), and also Serial No. 42,134, filed August 2, 1948. Attention is directed also to our co-pending application, Serial No. 64,469, filed Dec. 10, 1948.

Complementary to the above aspect of the invention is our companion invention concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as theapplication of such chemical compounds, products, and the like, in various other arts and industries, along with the method for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. See our co-pending application, Serial No. 64,447, filed December 10, 1948.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil," roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oiland relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

Demulsification as contemplated in the present application in'ludes the preventive step of commingling the-demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

Briefly stated, the present process is concerned with the breaking or resolving of petroleum emulsions by means of certain esters which are, in turn, derivatives of specific synthetic products. These products are, in turn, the oxyalkylated derivatives of certain resins hereinafter specified.

Thus, the present process is concerned with breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a hydrophile ester in which the acyl radical is that of the fatty acid of a hydroxyacetylated drastically-oxidated ricinoleic acid compound selected from the class consisting of blown castor oil, blown triricinolein, blown diricinolein, blown monoricinolein, blown superglycerinated castor oil, superglycerinated blown castor oil, blown ricinoleic acid, blown polyricinoleic acid and blown castor oil estolides, and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (B) an oxyalkylation-susceptible, fusible, organic solventsoluble, water-insoluble phenolaldehyde resin; said resin being derived by re-" action between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R10) n, in which R1 is a member selected from the class consisting of ethylene radicals; propylene radicals, butylene cylphenol.

radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said ester, as well as said oxyalkylated resin, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

For purpose of convenience what is said hereinafter will be divided into four parts. Part 1 will be concerned with the production of the resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; Part 3 will be concerned with the conversion of the immediately aforementioned derivative into a total or partial ester by reaction with an acid, an ester, or other functional derivative so as to obtain a compound of the kind preyiously specified and subsequently described in detail; andPart 4 will be concerned with the use of such esters as demulsifiers as hereinafter specified.

PART 1 As to the preparation of the phenol-aldehyde resins reference is made to our co-pending applications, Serial Nos. 8,730, and 8,731, both filed February 16, 1948, (both now abandoned). In such co-pending applications we described a fusible, organic solvent-soluble, water-insoluble resin polymer of the formula In such idealized representation n" is a numeral varying from 1 to 13 or even more, provided that the resin is fusible and organic solvent-soluble. R is a hydrocarbon radical having at least 4 and not over 8 carbon atoms. In the instant application R may have as many as 12 carbon atoms, as in the case of a resin obtained from a dode- In the instant invention it may be first suitable to describe the alkylene oxides employed as reactants, then the aldehydes, and ilnally the phenols, for the reason that the latter require a more elaborate description.

The alkylene oxides which may be used are the alpha-beta oxides having not more than 4 carbon atoms, to wit, ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene oxide, glycide, and methylglycide.

Any aldehyde capable of forming a methylol or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so long as it does not possess some other functional group or structure which will conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of an aqueous solution, for the production of the resins is particularly advantageous. Solid polymers of formaldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive. Furthermore, the higher aldehyde may undergo other reactions which are not desirable, thus introducing difliculties into the resiniflcation step. Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self-resinification when treated with strong acids or alkalies. On the other hand, higher aldehydes frequently beneficially affect the solubility and fusibility of a resin. This is illustrated, for example, by the different characteristics of the resin prepared from para-tertiary amylphenol and formaldehyde on one .hand, and a comparable product prepared from the same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle, solid, whereas the latter is soft and tacky, and obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. The employment of furfural requires careful control for the reason that in addition to its aldehydic function, furfural can form vinyl condensations by virtue of its unsaturated structure. The production of resins from'furfural for use in preparing reactants for the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes. in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, Z-ethylhexanal. ethylbutyraldehyde, heptaldehyde, and benzaldehyde. furfural and glyoxal. It would appear that the use of glyoxal should be avoided due to the fact that it is tetrafunctional. However. our experience has been that, in resin manufacture and particularly asdescribed herein,

apparently only one of the aldehydic functions enters into the resinification reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Needless to say. one can use a mixt re of two or more aldehydes although usually th has no advantage.

Re ins of the kind which are used as intermediates in this invention are obtained with the use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amine and quaternar ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts they enter into the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine'illustrates such a combination. In light of these various reactions it becomes difficult to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequen ly as to the difference between the use of an alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where different basic materials are employed. The basic materials employed include not only those previously enumerated but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids such as sodium acetate, etc.

Suitable phenolic reactants include the following: Para-tertiarybutylphenol; para-secondary-butylphenol; paratertiary-amylphenol; parasecondary-amylphenol; para teritaryhexylphenol; para-isooctylphenol; ortho phenylphenol; paraphenylphenol; ortho--benzylphenol; parabenzylphenol; and para-cyclohexylphenol, and

the corresponding orth-para substtiuted metacresols and 3,5-xyleno1s. Similarly, one may use paraor ortho-nonylphenol or a mixture, paraor ortho-decylphenol or a mixture, menthylphe- 1101, or paraor ortho-dodecllphenol. V

For convenience, the phenol has previously been referred toas monocyclic inorder to differentiate from fusednucleus polycyclic phenols, such as substtiuted naphthols. Specifically, "monocyclic is. limited to the nucleus in which the hydroxyl radical is attached. Broadly speaking, where a substituent is cyclic, particularly aryl, obviously in the usual sense such phenol is actually polycyclic although the phenolic hydroxyl is not. attached to a fused polycyclic nucleus. Stated another way, Dhenolsin which the hydroxyl group is directly attached to a condensed or fused polycyclic structure, are excluded. This 'matter, however, isclarified by the following consideration. The phenols herein contemplated for reaction may be indicated by the following formula:

in which R is selected from the class consisting of hydrogen atoms and hydrocarbon radicals having at least 4 carbon atoms and not more than 12 carbon atoms, with the proviso that one occurrence of R is thehydrocarbon substtiuent and the other two occurrences are hydrogen atoms, and with the further provision that one or both of the'3 and 5 positions may be methyl substituted.

The above formula possibly can be restated more conveniently in the following manner, to wit, that the phenol employed is of the following formula, with the proviso that R is a hydrocarbon substituent located in the 2,4,6 position, again with the provision as to 3 to 3,5 methyl substitution. This is conventional nomenclature, numbering the various positions in the usual clockwise manner, beginning with thehydroxyl position as one:

trade and oil solubility is of prime importance. l6

' phenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolfor'mald'ehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difliculty, while when a water-insoluble phenol is employed some modification is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large interfacial area. Once the reaction starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion of an organic sulfo-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydrochloric acid. For example, al kylated aromatic sulfonic acids are effectively employed. Since commercial forms of such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such alkali salt plus a small quantity of strong mineral acid, as shown in the examples below. If desired, such organic sulfo-acids may be prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a, small proportion of the phenol. In such cases where xylene isused as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfo-acid. Addition of a solvent such as xylene is advantageous as hereinafter described in detail. variation of procedure is to employ such organic sulfa-acids, in the form of their salts, in connection with an alkali-catalyzed resinification procedure. Detailed examples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin by the a d catalytic procedure is that, since a difunctional phenol is employed, an excess of an aldehyde, for instance formaldehyde, may be employed without too marked a change in conditions of reaction and ultimate product. There is usually little, if any, advantage, however, in using an excess over and above the stoichiometric proportions for the reason that such excess may be lost and wasted. For all practical purposes the molar ratio of formaldehyde to phenol may be limited to 0.9 to 1.2, with 1.05 as the preferred ratio, or sufiicient, at least theoretically, to convert the remaining reactive hydrogen atom of each terminal phenolic nucleus. Sometimes when higher aldehydes are used an excess of aldehydic reactant can be distilled off and thus recovered from the reaction mass. This same procedure may be used with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased over the simple stoichiometric ratio of one-to-one or thereabouts. With the use of alkaline catalyst it has been recognized that considerably increased amounts of formaldehyde may be used, as much as two moles of formaldehyde, for example, per mole of phenol, or even more, with the result that only a small partof such alde- Another hyde remains uncombined or is' subsequently liberated during resinification. Structures which have been advanced to explain such increased use of aldehydes are the following:

on on -o- :CUQm-Q-CH,Q

on on n c oH,-o-oH,- 4 H Such structures may lead to the production of cyclic polymers instead of linear polymers. For

this reason, it has been previously pointed out that, although linear polymers have by far the most important significance, the present invention does not exclude resins of such cyclic structures.

Sometimes conventional resiniilcation procedure is employed using either acid or alkaline catalysts to produce low-stage resins. Such resins may be employed as such, or may be altered or converted into high-stage resins, or in any event, into resins of higher molecular weight, by heating along with the employment of vacuum so as to 'split off water or formaldehyde, or both. Generally speaking, temperatures employed, particularly with vacuum, may be in the neighborhood of 175 to 250 C., or thereabouts.

It may be well to point out, however, that the amount of formaldehyde used may and does usu-' ally affect the length of the resin chain. Increasing the amount of the aldehyde, such as formaldehyde, usually increases the size or molecular weight of the polymer.

In the hereto appended claims there is specified, among other things, the resin polymer containing at least 3 phenolic nuclei. Such minimum molecular size is most conveniently determined as a rule by cryoscopic method using benzene, or some other suitable solvent, for instance, one of those mentioned elsewhere herein as a solvent for such resins. As a matter of fact, using the procedures herein described or any conventional resinification procedure will yield products usually having definitely in excess of 3 nuclei. In other words, a resin having an average of 4, 5 or 5 nuclei per unit is apt to be formed as a minimum in resinification, except under certain special conditions where dimerization may occur.

However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, etc., or some other suitable solvent which boils or refluxes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked excess of formaldehyde or other aldehyde, then the average size of the resin is apt to be distinctly over the above values, for example, it may average '7 to 15 units. Sometimes the expression lowstage resin or "low-stage intermediate is employed to mean a stage having 6 or 7 units or even less. In the appended claims we have used lowstage to mean 3 to '7 units based on average molecular weight.

The molecular weight determinations, of course, require that the product be completely soluble in the particular solvent selected as, for instance, benzene. The molecular weight determination of such solution may involve either the freezing point as in the cryoscopic method, or, less conveniently perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method for determining the molecular weights of resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins," page 157, Reinhold Publishing Co. 1947).

Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no catalyst. As far as resin manufacture per se is concerned, we prefer to use an acid catalyst, and particularly a mixture of an organic sulfo-acid and a mineral acid, along with a suitable solvent, such as xylene, as hereinafter illustrated in detail. However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is used in different stages of resinification. Resins so obtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., those referred to as high-stage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost-certain to produce further polymerization. For instance, acid catalyzed resins obtained in the usual manner and having a molecular weight indicating the presence of approximately 4 phenolic units or thereabouts may be subjected to such treatment, with the result that one obtains a resin having approximately double this molecular weight. The usual procedure is to use a secondary step, heating the resin in the presence or absence of an inert gas, including steam, or by use of vacuum.

We have found that under the usual conditions of resinification employing phenols of the kind here described, there is little or no tendency to form binuclear compounds, 1. e., dimers, resulting from the combination, for example, of 2 moles of a phenol and one mole of formaldehyde, particularly where the substituent has 4 or 5 carbon atoms. Where the number of carbon atoms in a substituent approximates the upper limit specifled herein, there may be some tendency to dimerization. The usual procedure to obtain a dimer involves an enormously large excess of the phenol, for instance, 8 to 10 moles per mole of aldehyde. Substituted dihydroxydiphenylmethanes obtained from substituted phenols are not resins as that term is used herein.

Although any conventional procedure ordinarily employed may be used in the manufacture 'of the herein contemplated resins or, for that matter, such resins may be purchased in the-open market. we have found it particularly desirable to use the procedures described elsewhere herein,

sequent examples are included, but it is to be understood the'h'ereindescribed invention is not concerned with the resins per se or with any par.-

ticular method of manufacture but is concerned with the use of reactants obtained by the subsequent oxyalkylation thereof. The phenol-aldehyde resins may be prepared in. any suitable manner.

Oxyalkylation, particularly oxyethylation which is the preferred reaction, depends on contact between a' non-gaseous phase and a gaseous phase. It can, for example, be carried out by melting the thermoplastic resin and subjecting it to treatment with ethylene oxide or the like, or by treating a suitable solution or suspension. Since the melting points of the resins are often higher than desired in the initial stage of oxyethylation. we have found it advantageous to use a solution or suspension of thermoplastic resin in an inert solvent such as xylene. Under such circumstances, the resin obtained in the usual manner is dissolved by heating in xylene under a reflux condenser or in any other suitable manner. Since xylene or an equivalent inert solvent is present or may be present during oxyalkylation, it is obvious there is no objection to having a solvent present during the resinifying stage if, in addition to being inert towards the resin, it is also inert towards the reactants and also inert towards water. Numerous solvents, particularly -of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, propyl benzene, mesitylene, decalin (decahydronaphthalene), tetralin (tetrahydronaphthalene), ethylene glycol diethylether, diethylene glycol diethylether, and tetraethylene glycol dimethylether, or mixtures of one or more. Solvents such as dichloroethylether, or dichloropropylether may be employed either alone or in mixture but have the objection that the chlorine atom in the compound may slowly combine with the alkaline catalyst employed in oxyethylation. Suitable solvents may be selected from this group for molecular weight determinations.

The use of such solvents is a convenient expedient in the manufacture of the thermoplastic resins, particularly since the solvent gives a more liquid reaction mass and thus prevents overheating, and also because the solvent can be employed in connection with a reflux condenser and a water trap to assist in the removal of water of reaction and also water present as part of the formaldehyde reactant when an aqueous solution of formaldehyde is used. Such aqueous solution, of course, with the ordinary product of commerce containing about 37 to 40% formaldehyde, is the preferred reactant. When such solvent is used it is advantageously added at the beginning of the resinification procedure'or before the reaction has proceeded very far. I

The solvent can be removed afterwards by distillation with or without the use of vacuum, and a final higher temperature can be employed to complete reaction if desired. In many instances it is most desirable to permit part of the solvent, particularly when it is inexpensive, e. g., xylene, to remain behind in a predetermined amount so as to have a resin which can be handled more conveniently in the oxyalkylation stage. If a more expensive solvent, such as decalin, is employed,

xylene or other inexpensive. solvent. may be added after the removal of 'decaiin, if desired. Inlpreparin'g resins from difunctional phenols it'f is common to employ reactants of technical, grade. The substituted phenols herein contem-; plated are usually. derived from hydroxybenzene. As a rule, suchsubstituted phenols are compara- 1 tively free from unsubstituted phenol. We have generally found that the amount present is considerably lessthan 1% and not infrequently in the neighborhood of of 1%, or even less. The amount ,of the usual trifunctional'phenol,

such as hydroxybenzene or metacresol, which can be tolerated is determined by the fact that actual cross-linking, if it takes place even infrequently, must notbe sufficientto cause insolubility at the completion of the resinification stage or the lack of hydrophile properties at the completion of the oxyalkylationstage. I

The exclusion of such trifunctional phenols as hydroxybenzene or metacresol is not based on the fact that the mere random or occasional inclusion of an unsubstituted phenyl nucleus in the resin molecule orin one of several molecules, for example, markedly alters the characteristics of the oxyalkylated derivative. The presence of a phenyl radical having a reactive hydrogen atom available or having a hydroxymethylol or a substituted hydroxymethylol group present is a potential source of cross-linking either during resinification or oxyalkylation. Cross-linking leads either to insoluble resins or to non-hydrophilic products resulting from the oxalkylation procedure. With this rationale understood, it is obvious that trifunctional phenols are tolerable only in a minor proportion and should not be present to the extent that insolubility is produced in the resins, or that the product resulting from oxyalkylation is gelatinous, rubbery, or at least not hydrophile. As to the rationale of resinification, note particularly what is said hereafter in differentiating between resoles, Novolaks, and resins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organic solvent-soluble resins are usually linear but may be cyclic. Such more complicated structure may be formed, particularly if a resin prepared in the usual manner is converted into a higher stage resin by heat treatcause cross-linking in a conventional resinification procedure, or in the oxyalkylation procedure, or in the heat and vacuum treatment if it is employed as part of resin manufacture.

Our routine procedure in examining a phenol for suitability for preparing intermediates to be used in practicing the invention is to prepare a resin employing formaldehyde in excess (1.2 moles of formaldehyde per mole of phenol) and using an acid catalyst in the manner described in Example laof our Patent 2,499,370 granted March 7, 1950. If the resin so obtained is solvent-soluble in any one of the aromatic or other solvents previously referred to, it is then subjected to oxyethylation. During oxyethylation a temperature is employed of approximately to C. with addition of at least 2 and advantageously up to 5 moles of ethylene oxide per phenolic hydroxyl. The oxyethylation is advantageously conducted so as to require from a few minutes up to to hours. If the product so obtained is solvent-soluble and self-dispersing or emulsifiable, or has emulsifying properties, the phenol is perfectly satisfactory from the standpoint of trifunctional phenol content. The solvent may be removed prior to the dispersibility or emulsifiability test. When a product becomes rubbery during oxyalkylation due to the presence of a small amount of trireactive phenol, as previously mentioned, or for some other reason, it may become extremely insoluble, and no longer qualifies as being hydrophile as herein specified. Increasing the size of the aldehydic nuc1eus,-for instance using heptaldehyde instead of formaldehyde, increases tolerance for trifunctional phenol.

The presence of a trifunctional or tetrafunctional phenol (such as resorcinol or bisphenol A) is apt to produce detectable cross-linking and insolubilization but will not necessarily do so, especially if the proportion is small. Resinification involving difunctional phenols only may also 'produce insolubilization, although this seems to be an anomaly or a contradiction of what is sometimes said in regard to resinification reactions involving difunctional phenols only. This is presumably due to cross-linking. This appears to be contradictory to what one might expect in light of the theory of functionality in resinification. It is true that under ordinary circumstances, or rather under the circumstances of conventional resi manufacture, the procedures employing difunctional phenols are very apt to, and almost invariably do, yield solventsoluble, fusible resins. However, when conventional procedures are employed in connection with resins for varnish manufacture or the like, there is involved the matter of color, solubility in oil, etc. When resins of the same type are manufactured for the herein contemplated purpose, i. e., as a raw material to be subjected to oxyalkylation, such criteria of selection are no longer pertinent. Stated another way, one may use more drastic conditions of resinification than those ordinarilyemployed to produce resins for the present purposes. Such more drastic conditions of reunification may include increased amounts of catalyst, higher temperatures, longer time of reaction, subsequent reaction involving heat alone or in combination with vacuum, etc. Therefore, one is not only concerned with the resinification reactions which yield the bulk of ordinary resins from difunctional phenols but also and particularly with the minor reactions of ordinary resin manufacture which are of importance in the present invention for the reason that they occur under more drastic conditions of resinification which may be employed advantageously at times and they may lead to crosslinking.

In this connection it may be well to point out that part of these reactions are now understood or explainable to a greater or lesser degree in light of a most recent investigation. Reference is most recent and-most up-to-date investigations is pertinent to the present invention insofar that much of it is referring to resinification involving difunctional phenols.

For the moment, it may be simpler to consider a most typical type of fusible resin and forget for the time that such resin, at least under certain circumstances, is susceptible to further complications. Subsequently in the text it will be pointed out that cross-linking or reaction with excess formaldehyde may take place even with one of such most typical type" resins. This point is made for the reason that insolubles must be avoided in order to obtain the products herein contemplated for use as reactants.

The typical type" of fusible resin obtained from a para-blocked or ortho-blocked phenol is clearly differentiated from the Novolak type or resole type of resin. Unlike the resole type, such typical type" para-blocked or ortho-blocked phenol resin may be heated indefinitely without passing into an infusible stage, and in this respect is similar to a Novolak. Unlike the Novolak type the addition of a further reactant, for instance, more aldehyde, does not ordinarily alter fusibility of the difunctional phenol-aldehyde type resin; but such addition to a Novolak causes cross-linking by virtue of the available third functional position.

What has been said immediately preceding is subject to modification in this respect: It is well known, for example, that difunctional phenols, for instance, paratertiaryamylphenol, and an aldehyde, particularly formaldehyde, may yield heat-hardenable resins, at least under certain conditions, as for example the use of two moles of formaldehyde to one of phenol, along with an alkaline catalyst. This peculiar hardening or curing or cross-linking of resins obtained from difunctional phenols has been recognized by various authorities.

' knowledge of the subject, and employing preliminary, exploratory routine examinations as herein indicated, there is not the slightest difficulty in preparing a very large number of resins of various types and from various reactants, and by means of difierent catalysts by different procedures, all of which are eminently suitable for the herein described purpose.

madev to the researches of Zinke and his co- Now returning to the thought that cross-linking can take place, even when difunctional phenols are used exclusively, attention is directed to the following: Somewhere during the course of resin manufacture there may be a potential cross-linking combination formed but actual cross-linking may not take place until the subsequent stage is reached, 1. e., heat and vacuum stage, or oxyalkylation stage. This situation may be related or explained in terms of a theory of flaws, or Lockerstellen, which is employed in explaining flaw-forming groups due to the fact that a CHaOH radical and H atommay not lie in the same plane in the manufacture of ordinary phenol-aldehyde resins;

Secondly, the formation or absence of formation of insolubles may be related to the aldehyde used and the ratio of aldehyde,'particularly formaldehyde, insofar thata slight variation -may, under circumstances not understandable, produce insolubilization. The formation of the insoluble resin is apparently very sensitive to the quantity of formaldehyde employed and a silght increase in the proportion of formaldehyde may lead to the formation of insoluble gel lumps. The cause 1 of insoluble resin formation is not clear, andnothing is known as 'to the structure of these resins.

All that has been said previously herein as regards resinification has avoided the specific reference to activity of a methylene hydrogen atom. Actually there is a possibility that under some drastic conditions cross-linking may take place through formaldehyde addition to the methylene bridge, or some other reaction involving a methylene hydrogen atom.

Finally, there is some evidence that, although the meta positions are not ordinarily reactive, possibly at times methylol groups or the like are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant. In other words, a phenol-aldehyde resin which is thermoplastic and solvent-soluble, particularly if xylene-soluble, is perfectly satisfactory even though retreatment -with more aldehyde may change its characteristics markedly, in regard to both fusibility and solubility. Stated anotherway, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactants, it is to be noted that they are thermoplastic phenol-aldehyde 'resins derived from difunctional phenols and are clearly distinguished from Novolaks or resoles. When these resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparatively fluid at 110 to 165 C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

Reference has been made to the use of the word fusible. Ordinarily a thermoplastic resin is identified as one which can be heated repeatedly andstill not lose its thermoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heating may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the present invention is concerned, it is obvious that a resin to be suitable need only be sufiiciently fusible to permit processing to produce our oxyalkylated products and not yield insolubles or cause insolubilization or gel formation, or rubberiness, as previously described. Thus resins which are, strictly speak.- ing, fusible but not necessarily thermoplastic in the most rigid sense that such terminology would be applied to the mechanical properties of a resin, are useful intermediates. The bulk of all fusible resins of the kind herein described are thermoplastic. i

The fusible or thermoplastic resins, or solventsoluble resins, herein employed as reactants, are

water-insoluble, or have noappreciable hydrophile properties. The hydrophile property is introduced by oxyalkylationl In the hereto appended claims and elsewhere the expresion watar-insoluble is used to point out this characteristic of the resins used.

In the manufacture of compounds herein employed, particularly for demulsification, it is obvious that the resins can be obtained by one of a number of procedures. In the first place, suitable resins are marketed by a number of companies and can be purchased in the open 'market; in the second place, there are a wealth of examples of suitable resins described in the literature. The third procedure is to follow the directions of the present application.

The polyhydric reactants, i. e., the oxyalkylation-susceptible, water-insoluble, organic solventsoluble, fusible, phenol-aldehyde resins derived from difunctional phenols, used as intermediates to produce the products used in accordance with the invention, are exemplified by Examples Nos. 1a. through 1030. of our Patent 2,499,370, granted March 7, 1950, and reference is made to that patent for example of the oxyalkylated resins used as intermediates.

Previous reference has been made to the use of a single phenol as herein specified, or a single reactive aldehyde, or a single oxyalkylating agent. Obviously, mixtures of reactants may be employed, as for example a mixture of para-butylphenol and para-amylphenol, or a mixture of para-butylphenol and para-hexylphenol, or para-,- butylphenol and para-phenylphenol. It is extremely diflicult to depict the structure of a resin derived from a single phenol. When mixtures of phenols are used, even in equimolar proportions, the structure of the resin is even more indeterminable. In other words, a mixture involving para-butylphenol and para-amylphenol might have an alternation of the two nuclei or one might have a series of butylated nuclei and then a series of amylated nuclei. If a mixture of aldehydes is employed, for instance, acetaldehyde and butyraldehyde, or, acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure of the resin becomes even more complicated and possibly depends on the relative reactivity of the aldehydes. ,For that matter, one might be producing simultaneously two different resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish off with propylene oxide. It is understood that the oxyalkylated derivatives of such resins, derived from such plurality of reactants, instead of being limited to a single reactant from each of the three classes, is contemplated and here included for the reason that they are obvious variants.

PART 2 Having obtained a suitable resin of the described, such resin is subjected to treatment with a low molal reactive alpha-beta olefin oxide so as to render the product distinctly hydrophile in nature as indicated by the fact that it becomes self-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties. The olefin oxides employed are characterized by the fact that they contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide. Glycide may be, of course, considered as a hydroxy propylene oxide and methyl glycide as a hydroxy butylene oxide. In any event, however, all such reactants contain the reactive ethylene oxide rin and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing effect of the oxide is directly proportional to the percentage of oxygen present, or speciflcially, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surfaceactive properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one of several propylene oxide or butylene oxide molecules have been attached to the resin molecule, oxyalkvlation may be satisfactorily continued using the more favorable members fthe class, to produce the desired hydrophile product. Used alone, these two reagents may in some cases fail to produce sufficiently hydrophile derivatives because of their relatively low oxygencarbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, and propylene oxide is more effective than butylene oxide. Hydroxy propylene oxide (glycide) is more effective than propylene oxide. Similarly, hydroxy butylene oxide (methyl glycide) is more effective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind from which the initial reactants used in the practice of the present invention are prepared is advantageously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% and 2%. The temperature employed may vary from room temperature to as high as 200 C. The reaction may be conducted with or without pressure, i. e., from zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups.

It may be necessary to allow for the acidity of a resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such as sulfuric acid is used to catalyze the resiniflcation reaction, presumably after being converted into a sulfonic acid, it may be necessary and is usually advantageous to add an amount of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount as the alkaline catalyst.

It is advantageous to conduct the oxyethylation in presence of an inert solvent such as xylene, cymene, decalin, ethylene glycol diethylether, diethyleneglycol diethylether, or the like, although with many resins, the oxyalkylation proceeds satisfactorily without a solvent. Since xylene is cheap and may be permitted to be present in the final product used as a demulsifier, it is our preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating agent is used. Under such circumstances it may be necessary at times to use substantial pressures to obtain effective results, for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduction of approximately 2 or 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a definite drop in the hardness and melting point of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively soft and solvent-free, can be reacted further in the usual manner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with such solvent present and then eliminate the solvent by distillation in the customary manner.

Another suitable procedure is to use propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the powdered resin in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree.

After a solution has been obtained which represents the original resin dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner.

Attention is directed to the fact that the resins herein described must be fusible or soluble in an organic solvent. Fusible resins invariably are soluble in one or more organic solvents such as those mentioned elsewhere herein. It is to be emphasized, however, that the organic solvent employed to indicate or assure that the resin 17 meets this requirement need not be the one in oxya1kylation. Indeed, solvents which are sus-.

ceptible .to oxyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and alcohol-ethers. However.

where a. resin is soluble in an organic solvent,

there are usually. available other organic solvents which are not susceptibleto oxyalirylation, use ful for the oxyalkylationsten' In any event, the

organic solvent-soluble resin can be finely pow-- dered, for instance to 100 to 200 mesh; and a slurry or suspension prepared in xylene or the like, and subjected to oxyalkylation. The fact that the resin is soluble in an organic solvent or the fact that it is fusible means that it consists of separate molecules. Phenol-aldehyde resins 18*- Allthatone needto-doisto water-in-oil type (usually the former) but, in

any event, is due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We preqfer simply to use the xylene diluted derivatives,

which are described elsewhere, for this test rather than evaporate the solvent and employ any more 1 elaborate tests, if the solubility is not suflicient of the type herein specified possess reactive hy.-

droxyl groups and are oxyalkylation susceptible. Considerable of what is said immediately here inafter is concerned with ability to vary the hy:

drophile properties of the hydroxylated inter mediate reactants from minimum hydrophile properties to maximum hydrophile properties. Such properties in turn, of course, are effected subsequent y by the acid employed for esteriflcation and the quantitative nature of the esterification itself, i. e., whether it is total or partial. It may be well, however, to point out what has been said elsewhere in regard to the hydroxylated opment of some property which makes it inherently different from the two reactants from which the derivative ester is obtained.

Referring to the hydrophile hydroxyla'ted intermediates, even more remarkable and equally diflicult to explain, are the versati ity and the utility of these compounds considered as chemical reactants as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the point where two ethyleneoxy radicals or moderately in excess thereof are introduced per phenolic hydroxyl. Such minimum hydrophile property or sub-surface-activity or minimum surface-activity means that the product shows at least emulsifying properties or self-dispersion in cold or even in warm distilled water (15 to 40 C.) in concentrations of 0.5% to 5.0%. These materials are generally more soluble in cold water than warm 1 water, and may even be very insoluble in boiling water. Moderately high temperatures aid in reducing the viscosity of the so ute under examination. Sometimes if one continues to shake a hot solution, even though cloudy or containing an insoluble phase, one finds that solution takes place to give a homogeneous phase as the mixture cools. Such self-dispersion tests are conducted in the absence of an insoluble solvent.

When the hydrophile-hydrophobe balance, is above the indicated minimum'(2 moles of ethylene oxide per phenolic nucleus or the equivalent) but insufllcient to give a sol as described immediately preceding, then, and in that event hydrophlle properties are indicated by the fact that one can produce an emulsion by having present 10% to 50% of an inert solvent such as xylene.

to permit the simple sol test in water previously noted. 7

If the product is not readily water soluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethylene glycol diethylether, with a little acetone, added if required, making a rather concentrated solution, for instance 40% to 50 and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 0.5% to 5.0%

' strength solution. If the product is self-dispersing (i. e., if the oxyalkylated product is a liquid or a liquid solution self-emulsifiable), such sol or dispersion is referred to as at least semi-stable; in the sense that sols, emulsions, or dispersions; prepared are relatively stable, if they remainat least for some period of time, for instance 30 min: utes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 C.) Needless to say, a test can be made in presence of an insoluble solvent such as 5% to 15% of xylene, as noted in previous examples. If such mixture,i. e., containing a water-insoluble solvent, is at least semi-stable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements hereinafter described. One outstanding characteristic property indicating surfaceactivity in a material is the ability to form a permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in the lower and intermediate stages of oxyalkylation.

Allowance must be made for the presence of a I solvent in the final product in relation to the hydrophile properties of the final product. The

principle involved in the manufacture of the herein contemplated compounds for use as polyhydric reactants, is based on the conversion of a hydrophobe or non-hydrophile compound or mixture of compounds into products which are distinctly hydrophile, at least to the extent that they have emulsifying properties or are self emulsifying; that is, when shaken with waterthey produce stable or semi-stable suspensions, or, in the presence of a water-insoluble solvent, such as xylene, an emulsion. In demulsification, 1 it is sometimes preferable to use a product hav ing markedly enhanced hydrophile properties over and above the initial stage of self-emulsifiability, although we have found that with products of the type used herein, most efficacious results are obtained with products which do not have hydrophile properties beyond the' stage of self-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface active agents. Such conventional surface-activity may be measv have axylenesolu-f tion within the ran e or so. to .90 parts by. w ight:

of oxyalkylated derivatives'and 50 to .10 parts'by I weight of xylene and mix'suchsolution with one, twoor three times its volume of distilled water and shake vigorously so as to obtain an'emulsion' v which niay be of the oil-in-water type or the ured by determining the surface tensionand the interfacial tension against paraffin oil or the like. At the initial and lower stages of oxyalkylation, surface-activity is not suitably determined in this same manner but one may employ an emulsiilcation test. Emulsions come into existence as a rule through the presence of a surface-active emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oil-in-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylatiom'the so-called "sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably suilicient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of distlled water used is at least slightly in excess of the volume of. miene solution and also if shaken vigorousLv. At times, particularly in the lowest stage of oxyalkylation, one may obtain a waterin-xylene emulsion (water-in-cil type) which is apt to reverse on more vigorous shaking and furweight indicating about 4% units per resin molecule. Such resin, when diluted with an equal weight of :wlene, will serve to illustrate the above emulsiflcation test.

In a few instances, the resin may not be sumciently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of, xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surfaceactive characteristics in the polyhydric reactants used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, com arison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The resence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsiflcation. For this reason, if it is desirable to determine the approxthen it is better to eliminate the xylene or equiv-- alent from a small portion of the reaction mixture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other 'cases, the first objective indication of hydrophile properties may he the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsiflcation tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the effectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2 moles per phenolic nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the. aldehyde such as formaldehyde. It is well known that the size and nature or structure of the resin polymer obtained vari.s somewhat with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating step, contain 3 to 6 or 7 phenolic nuclei with approximately 4 or 5% nuclei as an average. More drast c cond tions of resiniflcation yield resim of greater chain length. Such more intensive resiniiication is a conventional procedure and may be employed if desired. Molecular weight, of course, is measured by any suitable procedure, particularly by cryoscopic methods; but using the same reactants and using more drastic cond tions of re iniflcation one usually finds that higher molecular weights are ind cated by higher melting points of the resins and a tendency to decreased solubility. See what has been said elsewhere herein in regard to a secondary step involving the heating of a resin with or without the use of vacuum.

We have previously po nted out that e ther an alkaline or acid catalyst is advantageously used in preparing the resin. A combination of catalysts is somet mes used in t o stages: for instance, an alkaline catalyst is sometimes employed in a first stage. follo ed bv n-utrali ation and addit on of a small amount of ac d catalyst in a second stage. It is gener lly belie ed that even in the presence of analkaline catalyst, the

number of moles of aldehyde. such as formaldehyde, must be greater than the mole: of phenol employed in order to introduce methylol groups imate point where self-emulslflcation begins, 76 in the intermediate stage. There is no indicaauam possible that such groups may appear in the film ished resins prepared solely with an alkaline catalyst: but we have never been able to confirm this fact in an examination of a large number of resins prepared by ourselves. Our preference, however, is to use an acid-catalyzed resin, particularly employing a formaldehyde-to-phenol ratio 010.95 to 1.20 and, as far as we have been able to determine, such resins are free from methylol groups. As a matter of fact, it is probable that in acid-catalyzed resiniflcations, the methylol structure may, appear only moment'arily at the verybeginning of the reaction and in all probability is converted at once into amore complex structure during the intermediate sta e.

One procedure which can be em loyed in the use of anew resin to prepare polyhydric reactcut: for use in the preparat on of compounds employed in the present invention. is to determine the hydroxvlyalue by the Verley-Biil ing method or its equiva ent. Th re n as s ch. or in the form of a. solution as described, is then treated with ethylene ox de in presence of 0.5% to 2% of sodium methyl te as a catalyst in stepwise fashion, The cond tions of reaction, as far astime or oer cent are concerned. are within the ran e previously indicated. W th suitable agitation the ethylene oxide. if added in molecular pro ortion, combines within a comparatively short t me, for instance a few minutes to 2 to 6 hours, but in some instances requires as much as 8 to 2 hours. Ausef l tem erature range is from 125 to 225 C. The cnmnletion of the reaction of ear-h addition'of eth lene ox de in step-wise fashion is usually indicated by the reduction or elimination of press re. An amount convenientl used for each add tion is generally equivalent to a mole or two m les of ethylene oxide per hydroxyl radical. when the amount of ethylene oxide added is equivalent to approximately 50% by weight of the original resin, a

sample is tested for incipient hydrophile properties by simply shaking up in water as is, or after the elimination of the solvent if a solvent is present. The amount of ethylene ox de used to obtain a useful demulsifying agent as a rule varies from 70% by weight of the original resin to as much as live or six times the we ght of the original resin. In the case of a resin derived from para-tertiary butylphenol, as little as 50% by wei ht of ethylene oxide may give suitable solubility. With propylene oxide, 'even a. greater molecular proportion is required and sometimes a resultant of onlylimited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide.- The hydroxvlated alkylene oxides are more efl'ective in solubilizing pro erties than t e comparable. compounds in which no hydroxyl is present.

Attention is directed to thefact that in the subsequent examples reference is made to the stepwise addition of the alkylene oxide, such as ethylene oxide. It is understood, of course, there is no objection to the continuous addition of 'alkylene oxide'until the desired stage of reaction is reached. In fact, there maybe less of a hazard involved and it is often advantageous to add the akylene oxideslowly in a continuous stream and in such amount as to avoid exceeding the higher pressures noted in the various examples or elsewhere.-

It may be well to emphasize the fact that when resins are produced from difuncticnal phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft or pitch-like resin at ordinary temperatures. Such resins become comparatively fluid at to C. as a rule, and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent. v

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation. and particularly oxyethylation. What has been said previously is submitted. primarily to emphasize the fact that these remarkable oxyalkylated resins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these polyhydric alcohols in a surface-active or subsurface-active range without examining them by reaction with a number of the typical acids herein described and subsequently examining the resultant for utility, either in demulsiflcation or in some other art or industry as referred to elsewhere, or as a reactant for the manufacture of more complicated derivatives. A few simple laboratory tests which can be conducted in a routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2 to 1; 6 to 1; 10 to 1: and 15 to 1. From a sample of each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in distilled water. as previously indicated. A mere examination of such series wi l generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the solventfree product, then one should test its capacity to form an emulsion when admixed with xylene or other insoluble solvent. If neither test shows the required minimum hydrophile property, repetition using 2 to 4 moles per phenolic nucleus .Such moderate hydrophile character is indicated bythe fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol when viewed in a comparatively thin layer, for instance the depth of a test tube. Ultimate hydrophile character is usually shown at the 15 to 1 ratio test in that adding a small amount of an insoluble solvent, for instance 5% of xylene, yields a product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken. is an excellent test for surface activity. Previous reference has been made to the" fact that other oxyalkylating agents may require the use of increased amounts of alkylene oxide. However, if one does not even care to go to the trouble of calculating molecular weights, one can 7 simply arbitrarily prepare compounds containing ethylene oxide equivalent to about 50% to 75% by weight, for example 65% by weight, of the resin to be oxyethylated; a second example using approximately 200% to 300% by weight, and a third example using about 500% to 750% by weight, to explore the range of hydrophile-hydrophobe balance.

A practical examination of the factor of oxyalkylation level can be made by a very simple test using a pilot plant autoclave having a capacity of about to gallons as hereinafter described. Such laboratory-prepared routine compounds can then be tested for solubility and, generally speaking, this is all that is required to give a suitable variety covering the hydrophile-hydrophobe range. All these tests, as stated, are intended to be routine tests and nothing more. They are intended to teach a person, even though unskilled in oxyethylation or oxyallwlation, how to prepare in a perfectly arbitrary manner. a series of compounds illustrating the hydrophile-hydrophobe range.

If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are available, one might have to make certain determinations in order to make the quickest approach to the appropriate oxyalhlatlon range. For instance, one should know (a) the molecular size, indicating the number of phenolic units; (b) the nature of the aldehydic residue, which is usually CH2; and (c) the nature of the substituent, which is usually butyl. amyl, or phenyl. With such information one is in substantially the same position as if one had gersonally made the resin prior to oxyethyla- For instance, the molecular weight of the internal structural units of the resin of the following over-simplified formula:

0H g on OH @1011) (n=1 to 13. or even more) is given approximately by the formula: (Moi. wt. of phenol 2) plus mol. wt. of methylene or substituted methylene radical. The molecular weight of the resin would be n times the value for the internal limit plus the values for the ,terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring internal unit except that it has one extra hydrogen. The right-hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resins molecular weight is given approximately by taking (n plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the structure shown, this calculation will be in error by several per cent; but as it grows larger, to contain 6, 9, or 12 phenolic nuclei, the formula comes to be more than satisfactory. Using such an approximate weight, one need only introduce, for example, two molal weights of ethylene oxide or slightly more, per phenolic nucleus, to produce a product of minimal hydrophile character. Further oxyalkylation gives enhanced hydrophile character. Although we have prepared and tested a large number of oxyethylated products of the type described herein, we have found no instance where the use of less than 2 moles of ethylene 24 oxitge per phenolic nucleus gave desirable produc Examples 1b through 181), and the tables which appear in columns 51 through 56 of our said Patent 2,499,370 illustrate oxyalkvlation products from resins which are useful as intermediates for producing the esterified products used in accordance with the present application, such examples giving exact and complete details for carrying out the oxyalkylation procedure.

The resins, prior to oiwallwlatlon, vary from tacky, viscous liquids to hard, high-melting solids. Their color varies from a light yellow through amber, to deep red or even almost black. In the manufacture of resins, particularly hard resins, as the reaction progresses the reaction mass frequently goes through a liquid state to a sub-resinous or semi-resinous state, often characterized by being tacky or sticky, to a final complete resin. As the resin is subjected to oxyalkylation these same physical changes tendtotake place in reverse. If one starts with a solid resin,

oxyalkylation tends to make it tacky or semiresinous and further oxyalkylation makes the tackiness disappear and changes the product to a liquid. Thus, as the resin is oxyalkylated it decreases in viscosity, that is, becomes more liquid or changes from a. solid to a liquid, particularly when it is converted to the water-dispersible or water-soluble stage. The color of the oxyalkylated derivative is usually considerably lighter than the original product from which it is made, varying from a pale straw color to an amber or reddish amber. The viscosity usually varies from that .of an oil, like castor oil, to that of a thick viscous sirup. Some products are waxy. The presence of a solvent, such as 15% xylene or the like, thins the viscosity considerably and also reduces the color in dilution. No undue significance need be attached to the color for the reason that if the same compound is prepared in glass and in iron, the latter usually has somewhat darker color. If the resins are prepared as cus-' tomarily employed in varnish resin manufacture, i. e., a procedure that excludes the presence of oxygen during the resiniflcation and subsequent cooling of the resin, then of course the initial resin is much light in color. We have employed some resins which initially are almost waterwhite and also yield a lighter colored final product.

Actually, in considering the ratio of alkylene oxide to add, and we have previously, pointed out that this can be predetermined using laboratory tests, it is our actual preference from a practical standpoint'to make tests on a small pilot p ant scale. Our reason for so doing is that we make one run, and only one, and that we have a complete series which shows the progressive efiect of introducing the oxyalkylatlng agent, for instance, the ethyleneoxy radicals. Our preferred procedure is as follows: We prepare a suitable resin, or for that matter, purchase it in the open market. We employ 8 pounds of resin'and 4 pounds of xylene and place the resin and xylene in a suitable auto clave with an open reflux condenser. We prefer to heat and stir until the solution is complete. We have pointed out that soft resins .which are fluid or semifluid can be readily prepared in various ways, such as the use of ortho-tertiary amylphenol, ortho-hydroxydiphenyl, orthodecylphenol, or' by the use of higher molecular weight aldehydes than formaldehyde. If such resins are used, a solvent need not be added but maybe added as a matter ofconvenience or for comparison, ifdesired. We then add a catalyst, for instance, 27% of caustic sode, in .the form of a 20% to solution and remove the water of solution or, formation. We then shut off the reflux condenser and use the equipment as an autoclave only, and. oxyethylate untila total of pounds of ethylene oxide have been added, equivalent to 750% i of the original resin. We" prefer a temperature of about 150 C. to 175 0. We alsotake samples at intermediate points as indicated in the following table:

Pounds of Et'iylenc Percentages Oxide Added pel S-pound Batch Oxyethylation to 750% can usually be completed within 30 hours and frequently more quickly. The samples taken are rather small, for instance, 2 to 4 ounces, so that no correction need be made in regard to the residual reaction mass. Each sample is divided in two. One-half the sample is placed in an evaporating dish on the steam bath overnight so as to eliminate the mlene. Then 1.5% solutions'are prepared from both series of samples, 1. e., the series with xylene present and the series with xyleneremoved. Mere visual examination of any samples .in solution may be suflicient to indicate hydrophile character or surface, activity, 1. e., the product is soluble, forming a colloidal sol, or the aqueous solution foams or shows emulsifying property. All these properties are related through adsorption at the interface, for example, a gas-liquid interface or a liquid-liquid interface. If desired, surface activity can be measured in any one of the usual ways using a Du Nouy tensiometer or dropping pipette, or any other procedure for measuring interfacial tension. Such tests are conventional and require no further description. Any compound having sub-surface activity, and all derived from the same resin and oxyalkylated to a greater extent, 1. e., those having a greater proportion of alklylene oxide, are useful as polyhydric reactants for the practice of this invention.

Another reason why we prefer to use a pilot plant test of the kind above described is that we can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydroxybenzene of metacresol satisfactorily. Previous reference has been made to the fact thatone can conduct a laboratory scale test which will indicate whether or not a resin, although soluble in solvent, will yield an insoluble rubbery product. i. e., a product which is neither hydrophile nor surface-active, upon oxyethylation, particularly extensive oxyethylation. It is also obvious that one may have asolvent-soluble resin derived from a mixture of phenols having present 1% or 2% a: a trifunctional phenol which will result in an 26 insoluble rubber at the" ultimate stages of oxyethylation but not in the earlier stages. In other words, with resins from some such phenols, addition of 2' or 3 moles of the oxyalkylating agent per pnflllollc nucleus; particularly ethylene oxide, gives a surface-active reactant which isperfectly satisfactory, while more extensive oxyethylatlon yields an insoluble rubber, that is, an unsuitable reactant. It is obvious that this present procedure of evaluating trn'unctional phenol tolerance is more suitable tnanthe previous procedure.

It may be well to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyetlrylation, which would not appear in a normally conducted reaction. Reference has been made to cross-linking and its meet on solubility and also the fact that, if carried far enough, it causes incipient stringiness, then pronounced stringiness, usually followed by a semi-rubbery or rubbery stage. Inciplent stringiness, or even pronounced stringiness, or even the tendency toward a rubbery stage, is not oblectionable so long as the final product is still hydrophile'and at least sub-surface-active. Such material frequently is best mixed with a polar solvent, such as alcohol or the like, and preferably an alcoholic solution is used. The point which we want to make here, however, is this: Strmginess or rubberization at this stage may possibly be the result of etherification. Obviously if a dlfunctional phenol and an aldehyde produce a noncross-linked resin molecule and if such molecule is 'oxyalkylated so as to introducela plurality of hydroxyl groups in each molecule, then and in that event if subsequent etherification takes place,one is going to obtain cross-linking in the same general way that one would obtain cross-linking in other resinification reactions. Ordinarily there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree; However, suppose that a certain weight of resin is treated with an equal weight of, or twice its weight of, ethylene oxide. This may be done in a comparatively short time for instance,

at or C. in 4 to 8 hours, or even less. On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that'the reaction're' quired 4 or 5 times as long to introduce an equal amount of ethylene oxide employing the same temperature, then etherification might cause stringiness or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it may be well to repeat the experiment and reach the intermediate stage of oxyalkylation as rapidly as possible and then proceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etherification if it be caused by the extended time period.

It may be well to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethylation, of the thermoplastic resins herein described. This effect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presence of some accompanying water-insoluble solvent such as 10% to 15% of :wlene. Further 27 .o'xyalkylation, particularly omethylation, may then yield a product which, instead of giving a clear solution as previously. gives a very milky solution suggesting that some marked change has taken place. one explanation of the above change is that the structural unit indicated in the following way where 8n is a fairly large numher, for instance, 10 to 20, decomposes and an oxyalkylated resin representing a lower degree cryoscopic determinations for obvious reasons. Attention is directed to the fact that various organic solvents may be employed to verify that the resin is organic solvent-soluble. Such solubility test merely characterizes the resin. The particular solvent used in such test may not be suitable for a molecular weight determination and, likewise, the solvent used in determining molecular weight may not be suitable as a solvent of oxyethylation and a less soluble one, is gen- 10 during oxyalkylatiom, For solution of the oxerated and a cyclic polymer of ethylene oxide is produced, indicated thus:

. (canal-.1!

This fact, of course, presents no difliculty for the reason that oxyalkylation can be conducted nolic hydroxyls present in the resin molecule.

.In some instances, of course, such distribution cannot be uniform for the reason that we have not specified that the molecules of ethylene oxide, for example. be added in multiples of the units present in the resin molecule. This may be illustrated in the following manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum of two moles of ethylene oxide per phenolic nucleus are added, this would mean an addition of moles of ethylene oxide, but suppose that one added 11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously, even assuming the'most uniform distribution possible, some of the polyethyleneoxy radicals would contain 3 ethyleneow units and some would contain 2. Therefore, it is impossible to specify uni. form distribution in regard to the entrance of .the ethylene oxide or other oxyalkylating agent. For that matter, if one were to introduce moles of ethylene oxide there is no way to be certain that all chains of ethyleneoxy units would have 5 units; there might be some having, for example, 4 and 6 units, or for that matter 3 or '7 units. Nor-is there any basis for assuming that the number of molecules of the oxyalkylating agent added to each of the molecules of the resin is the same, or different. Thus, where formulae are given to illustrate or depict the oxyalkylated products, distributions of radicals indicated are to be statistically taken. We have, however, included specific directions and specifications in regard to the total amount of ethylene oxide, or total amount of any other oxyallqlating agent, to add.

In regard to solubility of the resins and the oxyalkylated compounds, and for that matter derivatives of the latter, the following should be noted. In oxyalkylation, any solvent employed should be non-reactive to the alkylene oxide employed.

Q [i1 Mormonc.

yalkylated compounds, or their derivatives a great variety of solvents may be employed, such as alcohols, ether alcohols, -cresols, phenols, ketones, esters, etc., alone or with the addition of water. Some of these are mentioned hereafter. We prefer the use of benzene or diphenylamine as a solvent in making cryoscopic measurements. The most satisfactory resins are those which are soluble in xylene or the like, rather than those which are soluble only in some other solvent containing elements other than carbon and hydrogen, for instance, oxygen or chlorine. Such solvents are usually polar, semipolar, or slightly polar in nature compared with xylene, cymene, etc.

Reference to cryompic measurement is concerned with the use of benzene or other suitable compound as a solvent. Such method will show that conventional resins obtained, for example, from para-tertiary amylphenol and formaldehyde in presence of an acid catalyst, will have a molecular weight indicating 3, 4, 5 or somewhat greater number of structural units pea molecule. If more drastic conditions of resiniflcatio'n are employed or if such low-stage resin is subjected to a vacuum distillation treatment as previously described, one obtains a resin of a distinctly higher molecular weight. Any molecular weight determination used, whether cryoscopic measurement or otherwise, other than the conventional cryoscopic one employing benzene, should be checked so as to insure that it gives consistent values on such conventional resins as a control. Frequently all that is necessary to make an approximation of the molecular weight range is to make a comparison with the dimer obtained by chemical combination two moles of the same phenol, and one mole of the same aldehyde under conditions to insure dimerization. As to the preparation of such dimers from substituted phenols, see Carswell, "Phenoplasts,"

page 31. The increased viscosity, resinous char-.

acter, and decreased solubility, etc., of the higher polymers in comparison with the dimer, frequently are all that is required to establish that the resin contains 3 or more structural units per molecule.

Ordinarily, the oxyalkylation is carried out in autoclaves provided with agitators or stirring devices. We have found that the speed of the agitation markedly influences the reaction time. In some cases, the change from slow speed agitation, for example, in a laboratory autoclave agitation with a stirrer operating at a speed of 60 to 200 This limitation does not apply to solvents used in R. P. M., to high speed agitation, with the stirrer 29 operating at 250 to 350 R. P. M., reduces the time required for oxyalkylation by about one-half to two-thirds. Frequently xylene-soluble products which give insoluble products by procedures employing comparatively slow speed agitation, give suitable hydrophile products when produced by similar procedure but with high speed agitation, as a result, we believe, of the reduction in the time required with consequent elimination or curtailment of opportunity for curing or etherization. Even if the formation of an insoluble product is not involved, it is frequently advantageous to speed up the reaction, thereby reducing production time, by increasing agitating speed. In large scale operations, we have demonstrated that economical manufacturing results from continuous oxyalkylation, that is, an operation in which the alkylene oxide is continuously fed to the reaction vessel, with high speed agitation, 1. e., an agitator operating at 250 to 350 R. P. M. Continuous oxyalkylation, other conditions being the same, is more rapid than batch oxyalkylation, but the latter is ordinarily more convenient for laboratory operation.

Previous reference has been made to the fact that in preparing esters or compounds of the kind herein described, particularly adapted for demulsiflcation of water-in-oil emulsions, and for that matter for other purposes, one should make a complete exploration of the wide variation in hydrophobe-hydrophile balance as previously referred to. It has been stated, furthermore, that this hydrophobe-hydrophile balance of the oxyalkylated resins is imparted, as far as the range of variation goes, to a greater or lesser extent to the herein described derivatives. This means that one employing the present invention should take the choice of the most suitable derivative selected from a number of representative compounds, thus, not only should a variety of resins be prepared exhibiting a variety of oxyalkylations, particularly oxyethylations, but also a variety of derivatives. This can be done conveniently in light of what has been said previously. From a practical standpoint, using pilot plant equipment, for instance, an autoclave having a capacity of approximately three to five gallons. We have made a single run by appropriate selections in which the molal ratio of resin equivalent to ethylene oxide is one to one, i to 5. 1 to 10, 1 to 15, and 1 to 20. Furthermore, in making these particular runs we have used continuous addition of ethylene oxide. In the continuous addition of ethylene oxide we have employed either a cylinder of ethylene oxide without added nitrogen, provided that the pressure of the ethylene oxide was sufiiciently great to pass into the autoclave, or else we have used an arrangement which, in essense, was the equivalent of an ethylene oxide cylinder with a means for injecting nitrogen so as to force out the ethylene oxide in the manner of an ordinary seltzer bottle, combined with the means for either weighing the cylinder or measuring the ethylene oxide used volumetrically. Such procedure and arrangement for injecting liquids is, of course, conventional. The following data sheets exemplify such operations, 1. e., the combination of both continuous agitation and taking samples so as to give five different variants in oxyethylation. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop immediately if there is any indication that reaction is stopped or, obviously, if reaction is a not started at the beginning of the reaction period. Since the addition of ethylene oxide is invariably an exothermic reaction, whether or not reaction has taken place can be judged in the usual manner by observing (a) temperature rise or drop, if any, (b) amount of cooling water or other means required to dissipate heat of reaction; thus, it there is a t-mperature drop without the use of cooling water or equivalent, or if there is no rise in temperature without using cooling water control, careful investigation should be made.

In the tables immediately following, we are showing the maximum temperature which is usually the operating temperature. In other words, by experience we have found that if the initial reactants are raised to the indicated temperature and then if ethylene oxide is added slowly, this temperature is maintained by cooling water until the oxyethylation is complete. We

have also indicated the maximum pressure that we obtained or the pressure range. Likewise, we have indicated the time required to inject the ethylene oxide as well as a brief note as to the solubility of the product at the end of the oxyethylation period. As one period ends it will be noted we have removed part of the oxyethylated mass to give us derivatives, as therein described;

the rest has been subjected to further treatment.

All this is apparent by examining the columns headed Starting mix," Mix at end of reaction, Mix which is removed for sample, and Mix which remains as next starter."

The resins employed are prepared in the manner described in Examples 1a through 103a of our said Patent 2,499,370, except that instead of being prepared on a laboratory scale they were prepared in 10 to 15-gallo'n electro-vapor heated synthetic resin pilot plant reactors, as manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania. and completely described in their Bulletin No. 2087, issued in 1947, with specific reference to Specification No. 71-3965.

For convenience, the following tables give the numbers of the examples of our said Patent 2,499,370 in which the preparation of identical resins on laboratory scale are described. It is understood that in the following examples, the change is one with respect to the size of the operation.

The solvent used in each instance was xylene. This solvent is particularly satisfactory for the reason that it can be removed readily by distillation or vacuum distillation. In these continuous experiments the speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subsequent tables it will be noted that if a comparatively small sample is taken at each stage, for instance, to one gallon, one can proceed through the entire molal stage .1 to 1, to 1 to 20, without remaking at any intermediate stage. This is illustrated by Example 15 previous sample.

Phenol for resin: Pam-tertiary amylphenol Aldehyde for resin: Formaldehyde Date, June 22, 1948 [Resin made in pilot plant size batch, approximately 25 ponnds, mrresponding to 3a of Patent 2,499,370 but this batch designated 1040.]

Mix Which is Mix Wbich Re- Mix 85 Egg- Removed [or main: as Next new Sample mm! Starting Mix Max. Max. Time Pressure, 'lempem Solubility lbaaqdn. ture,C. 1841119. kbs. Lbs Ibls. abs. Lbs girls. libs. Lbs Ibls. Ifibs. Lb o-es-'o-es-'o-es-'o-es-' vent in Eto vent in Eto vent in Eto vent in Ego First Stage Resin to Et0.-.. Molal Ratio 1:1.. 14.25 15.75 0 14.25 15.75 4.0 3.35 3.65 1.0 10.9 12.1 3.0 so 150 K I Ex. No. 1045.....

Second Stage Resin to EtO. Molal Ratio 1 Ex.No.105b....

Third Stage Resin to Et0.--.

}10.9 12.1 3.0 10.9 12.1 15.25 3.TI 4.17 5.31 7.13 7.93 9.94 158 K 8'1 Molal Ratio 1:10. Ex. No. 1065.....

Fourth Stage R881]! to Et0..--

Molal Ratio 1-15 Ex. No. l07b-.

Fifth Stage Resin to Et0....

Molal Ratio 1:20- Ex. No. l08b.....

2.04 7.60 1.80 2.04 10.2 M QB Phenol for resin: Nonylphenol- Aldehyde for resin: Formoldehyde Date, June 18. 1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 70a of Patent 2,499,370 but this batch designated 10941.]

Mixat End or which 18 ix which lie Startin Mix Removed for mains as Next 8 Reaction Sample Starter Mm Mu Time I Pressure, Temp erahm. Solubility gb Ifibs. Lbs Lbs. Lbs lbls. Ifib. Lbs 1811118. lfibs. Lbs .lbsl o es- 0 Reao eso esvent V Em vent in vent inf vent in no Fird one Rain to EtO- Molal Ratio 1: 115.0 15.0 0 15.0 15.0 3 5.0 5.0 1.0 10.0 10.0 2.0 50 150 1 8'1 Ex. No. 1095--- Stage Resin to Et0-. M018! Ratio 1:5.- 10 10 2.0 10 10 0.4 2.72 2.72 2.56 7.27 7.27 0.86 1M 14'! I D'l Ex. No. 1105.....

Third Stage Resin to EtO- Fourth Stage Resin to EtO- Mole] Ratio 1:15- 3.15 3.15 5.95 3.15 3.15 8.95 1.05 1.05 2.95 2.10 2.10 5.00 220 174 2% 8 Ex. No. 1125;---

Fifth Stage Resin to EtO. Mole] Ratio 1:20- 2. 10 2.10 6.00 2.10 2.10 8.) 220 183 #5 VB Ex. No. 1135".-- l

S-Soluble. 8T=Sllght tendency toward solubility. DT-Deflnite tendency toward solubility. VS-Very aolnblo.

I-Insoluble. ST=Slight tendency toward becoming soluble. FB-Fairly soluble. RB-Beadliy soluble. QB-Qnlte soluble.

Phenol for resin: Para-actylphenol Aldehyde for resin: Formaldehyde Date,J1me23,24,1948

{Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 8a of Patent 2,499,370 but this batch designated 11411;]

. Mix Which is Mix Which Re- 7 8 Starting Mix figg figg of Removed for mains as Next Sample Starter 6 Max. Max. Time 7 Pressure. 'lempsrahrs Solubility ga s. abs. Lbs lbls. iibs. Lbs Ibls. Ifibs. Lbs 2 Lbs. Lbs mm,

o eso es- 0 es- Resvent in no vent in Eto Vent in n vent in Eto Fire! Stone ResintoEtO- Molal Ratio 13.. 14.2 15.8 0 14.2 15.8 3.25 3.1 3.4 0.75 11.1 12.4 25 50 150 1%: NS 1 Ex. No. 1140-.- v

Second Stage Resin to mom. Molal Ratio 1:5- }11. 1 12 4 2. 5 11. 1 l2. 4 12. 5 7. 0 7. 82 7. 88 4. l 4. 58 4. 62 100 171 $4 88 Ex. No. 1150".--

Third Slug:

Rosin to EtO Molal Ratio 1:10- 6. 64 7. 36 0 6. 64 7.36 15. 0 120 190 1% 8 Ex. No. 1165"-.-

Four b Stage ResintoEtO- Molal Ratio 1 5. 4.40 4.9 0 4.4 4.9 14.8 400 160 )4 VS Ex. No. 1175.....

Fifth Stage Resin to EtO---- Molal Ratio 1:20. 4.1 4.58 4.62 4. 1 4.58 18. 52 260 172 34 VS Ex. No. 1181')---" S=Soluble. N 8 -Not soluble. SS-Bomewhat soluble. VS =Very soluble.

Phenol for resin: Menthylphenol Aldehyde for resin: Formaldehyde Date, July 8-13, 1948 v [Resin made in pilot plant size batch, approximately pounds, corresponding to 69a of Patent 2,409,370 but this batch designated 11941.]

' Mix Which is Mix Which Re- Starting Mix E Removed for mains as Next on Sample Starter Max.

Pressure, Tem gera- 2 Solubility Isms. abs. Lbs gbls. libs. Lbs lbls. Ifihs. Lbs gbls. 115. Lbs

oles- 0 es- 0 eso esvent in Eto vent in Eto vent in Etc vent in Eto Firat Stage Resin to Et0 1 Mulal Ratio 1:1 }l3.65 16.35 0 13.65 16. 3.0 9.55 11.45 2.1 4.1 4.9 0.9 150 1% NS Ex. No. 1190"--- Second Stage Resin to Et0 Molal Ratio 1:5-. 10 12 0 12 10. 4. 52 5. 42 4. 81 5. 48 6:58 5. 94 1%: V 8 Ex. No. 1205-.."

Third Stage Resin to Et0 v j Molal Ratio 1:1 5.48 6.58 5.94 5.48 6.58 10.85 90 160 $4 S Ex. No. 12111.

Fourth Stage Resin to Et0 Molal Ratio 1:15- 4. 1 4.9 0.9 4. 9 13. 180 171 194: Y5 Ex. No. 1221)-.-

Fifth Stage Resin to mom. Molal Ratio 1:2)- 3. 10 '3. 72 0. 68 3. 10 3. 72 13. 43 320 94 V S Ex. No. 1220..."

s-aoiume. NB-Not soluble. VB-Very soluble.

9,541,992 35 36 Phenol for resin: Para-secondary butylphenol Aldehyde for resin: Formaldehyde Date, July 14-15, 1048 [Resin made in pilot plant size batch. approximately 3 pounds. corresponding to 2o Patent 2,499,370 but this batch 1210.]

Mix which is Mix Which Re- Btexting Mix fig ggg of Removed (or mine as Next Sample Starter Max Max Prssnre. Temp &2? Solubility lslbii. at... Lb 1 2 libs. 1 .2 m. Lbs g o m.

0 as. e9 e9 es. vent in no vent in mo vent in no vent in no First Stage Resin to EtO M0111 Ratio 1: -}14.45 15.55 0 14. 15.55 4.25 5.07 0.38 1.75 8,48 0.17 2.50 00 150 91: N8 Ex. No. 1240.....-

Second Stage Resin to Et0 %oleIiRatlo1:5.-}8.48 0.17 2.50 8.48 0.17 15.0 583i 082i 11.05 2.55 2.85 4.05 05 188 )4 88 Third Stage Resin to Et0 Molal Ratio 1:10. 4.82l 5.18 0 4.82 5.18 14.25 no 183 M 8 Ex. No. 1265 Fouflh stoge Resin to EtO Mela] Ratio 1:15- 3.85 4.15 0 3.85 4.15 17.0 111 180 V8 Ex. No. 1275-.....

Fifth Stage Resin to Et0--. Mole] Ratio 1:20. 2.05 2.85 4.05 2.05 2.85 15.45 so 170 Ma V8 Ex. No. 1280-...--

8 -Soiubie. NB -Not soluble. 8B -Somewhnt soluble. VB-Very soluble.

Phenol for resin: Menthyl Aldehyde for resin: Propionaldehyde Date, August 12-13, 1948 [Resin made on pilot plant size batch, approximately 21 pounds, corresponding to 810 of Patent 2,400,370 but this batch designated 1200.]

Mix Which is Mix Which Re- Hterting Mix figg figg Removed [or mains as Next Sample Starter Mu. Mun

Pressure, Temp era- Solubility r g libs. 215. kbs. Lbs r g s. Ifibs. Lbs 1 .2 abs. Lbs

w w w w vent in Em vent in Em vent in Em vent in Em Hut flag:

ResintoEtO M0131 Ratio 1:1- 12.8 17. 128 17.2l 2.7.) 4.25 5.7 0.05 8.55 11.50 1.80 150 M N00 5010b. Ex. No. 12oo Second Stage ResintoEt0.. Mole! Ratio 1:5 8.55 11.50 1.80 8.55 11.50 0.3 4.78 0.42 5.2 3.77 5.08 4.10 100 170 )6 Somewhat Ex. N 0. 130b soluble.

Third Stage RosIntnEtOU Molai Ratio 1:10. 3.77 5.08 4.10 3.77 5.08 13.1 100 182 Ml Soluble. Ex. No. 131b Fourth Stage ResintoEtO M0131 Ratio 1:15. 5.2 7.0 5.2 7.0 17.0 3.10 4.17 10.13 2.10 2.83 0.87 m 182 M Veryeolnbie. Ex. No.132b

ResintoEt0. Molal Ratio 1:20. 210 2.83 5.87 2.10 2.83 0. N M vdyaohbb- Ex. No.133b

Phenol for resin: Para-tertiary amylphenol Aldehyde for resin; Furfural Date, August 27-31, 1948 [Resin madeon pilot plant size batch, approximately 25 pounds, corresponding to 4% of Patent 2,499,370 but this batch designated 2451340.]

1' Mix Whichis Mix Which Re- Starting Mix ggg figg 9 Removed for malnsasNext I Sample Starter Max. Max. Time Pressure. Tempgra- Solubility lgbi i. libs. r n lbls. gs. 1 2 a. Ibs. Lbs 1 2 s. libs. Lbs

t 0- 6S- eses- 1 vent in vent in vent in Eto vent in Em First Stage ResintoEtO MolalRatiol 11.2 18.0 11.2 18.0 3.5 2.75 4.4 0.85 8.45 13.6 2.65 120 135 54 Not soluble. Ex.No.134b-- Second Stage Resin to Eton... MoialRetio 1:5..- 8.45 13.6 2.65 8.45 13.6 1265 5.03 8.12 7.55 3.42 5.48 6.10 v 110 150 14 Somewhat Ex. No. 135b soluble;

Third Stage Resin to EtO. Molal Ralio1:l0 }4.5 8.0 4.5 6.0 14.5 2.45 4.35 7.99 2.05 3.65 6.60 ,180 163 )4 Soluble. Ex. No. 1365.....-

Fourth Stage Resin to EtO- I k I MolalRatiol:l5 3.42 5.48 5.10 3.42 5.48 15.10 180 188 $6 Verysoluble. Ex. No. 1375.-..--

Fiflh Stage Resin to EtO MolalRatiol 3.65 6.60 2.05 3.65 13.35 120 125 36 VerySoluble. Ex No.138b- Phenol for resin: Menthyl Aldehyde for-resin: Furfural Date, Sept. 23-24, 1948 [Resin made on pilot size batch. approximately 25 pounds, corresponding to 89:1 oi Patent 2,499,370 but this batch designated as 13911.]

Mix Which is Mix Which Re- Starting Mix figg figg Removed for mains as Next Sample Starter Max. Max

Pressure, Tempera- 3: Solubility lbs. sq. in. ture, G.

Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

Sol- Res- $3 801- Res- 5 33- 501- Resg2? s Res- 2? vent in vent in vent in vent in First Stage Basin Et0 Molal Ratio 1:1.-- 10. 17. 7 5 10. 25 17. 75 2. 5 2. 65 4. 0. 7. 6 13. 15 1. 150 )6 N01; Soluble. Ex. N0. 139b. 7

Second Stage Resin to Et0 Molal Ratio 1:5... 7.6 13.15 1.85 7.6 13.15 9.35 5.2 9.00 6.40 2.4 4.15 2.95 80 177 $6 Somewhat Ex. N 0. 140b soluble.

Third Stage Resin to Et0. Molal Ratio 1:10 4. 22 6. 98 4. 22 6.98 10. 0 90 165 if: Soluble. Ex. No. 1415-..-

Fourth Stage Resin to EtO Molal Ratio 1:15.- 3. 76 6. 24 3.76 6. 24 13. 25 100 171 A Very soluble. Ex. No. 142b Iijth Stage Resin to EtO Molal Ratio 1:20-- 2. 4 4. 15 2. 95 2. 4 4. 15 11. 70 90 H; Very Soluble. Ex. N 0. 143b Phenol for resin: Paro-octyl I Aldehyde for resin: Furjural Date, October Hl, 194s [Resin made on pilot plant size batch. approximately 25 pounds, corresponding to 4% of Patent 2.499.370 with 200 parts by weight of commercial para-octylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 14441.]

Mix Which is Mix Which Re- Starting Mix E 2: E3 3 Removed (or mains as Next 0 Sample Starter Ma Time Pressure, Temp era- Solubility r g l lgg. Lbs 1 .3 Lbs. Lbs ge s. m. Lbs I h s. abs. Lbs

Reso es o esvent in Eto vent in vent in Em vent in Eto Fin! Slim Resin to Et0.-.. Molal Ratio 1:1..- 12.1 18.6 12.1 18.6 3.0 5.38 8.5 1.34 6.72 10.32 1.66 an 150 M2 Insoluble. Ex. No. 1445"..-

Second Siege Slight tend- ResintoEt0.... cue to- Molal Ratio 1:5.- 9 14.25 9.25 14.25 11.0 3.73 5.73 4.44 5.52 8.52 6.56 100 177 M2 war he- Ex. No. 1450... coming soluble. Third Stage Rosin to Et0...- Molal Ratio 1:10. 6.72 10.32 1.66 6.72 10.32 14. 91 4.07 7.62 11.01 1.76 2.70 3.90 182 M Fairly solu- Ex. No. 1466.... I ble.

Fourth Stage Resin to Et0--.- Molal Ratio 1:15. 5.52 8.52 6.56 5.52 8.52 10. 81 176 it Readily sol- Ex. No. 1475.... uble.

Fiflh Stage Resin to EtO.... Molal Ratio 1:2). 1 75 2.70 3.90 1.75 2.70 8.4 so 100 54 Quite solu- Ex. No.148b-...- ble.

Phenol for resin: Para-phenyl Aldehyde for resin: Furfural Date, October 11- 1948 [Resin made on pilot lant size batch, approximately 25 pounds, corresponding to 42a 0! Patent 2,400,370 with 170 parts by weight oi commercial parap enylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 14911.]

Mix Which is Mix Which Re- Starting Mix figg figg Removed for mains as Next Sample Starter Max. Max. Time Pressure, Temp era' hm Solubility ga s. Ifibs. Lbs lbii. libs. Ibis. 116:3. Lbs 1 .11 5. libs. Lbs

o eso eso so esvent in Eto vent in Em vent in Eto vent in Eto First Stage Resin w Et0.. Molal Ratio 1:1.- 13.9 16.7 13.9 16.7 3.0 3.50 4.25 0.80 10.35 12.45 2.11 100 l6 Insoluble. Ex. N0. 1490--.-..

Second Stage Resin m EtO. 2 1 Molal Ratio 1 10.35 12.45 2.20 10.35 12.45 12.20 5.15 6.19 6.06 5.20 6.26 6.14 8) 183 is ac Ex No. 1500 War 50 ubiiity. Third Stage Resin to Et0...- Mole] Ratio 1:10- 8.90 10.7 8.00 10.70 19.0 5.30 6.38 11.32 3.60 4.32 7.68 90 193 A2 Fairly solu- .Ex. No. 151b-..-. ble.

Fourth Stage ResintoEt0---. Moial Ratio 1:15. 5 Z) 6.26 6.14 5.2) 6.26 10.6 100 171 )6 Readily sol- Ex. No. 1525.... uble.

Fifth Stage Resin to Et0.... Moial Ratio mo- 3.60 4.32 7.68 3.60 4.32 15.68 Sample somewhat rubbery and gelat- 210 2 Ex. No. 1530"..- inous but fairly soluble 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A HYDROPHILE ESTER IN WHICH THE ACYL RADICAL IS THAT OF THE FATTY ACID OF A HYDROXYACETYLATED DRASTICALLY-OXIDIZED RICINOLEIC ACID COMPOUND SELCTED FROM THE CLASS CONSISTING OF BLOWN CASTOR OIL, BLOWN TRIRICINOLEIN, BLOWN DIRICINOLEIN, BLOWN MONORICINOLEIN, BLOWN SUPERGLYCERINATED CASTOR OIL, SUPERGLYCERINATED BLOWN CASTOR OIL, BLOWN RICINOLEIC ACID, BLOWN POLYRICINOLEIC ACID AND BLOWN CASTOR OIL ESTOLIDES, AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID PHYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOLALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 